US20180057938A1 - Vapor-phase growth method - Google Patents
Vapor-phase growth method Download PDFInfo
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- US20180057938A1 US20180057938A1 US15/687,839 US201715687839A US2018057938A1 US 20180057938 A1 US20180057938 A1 US 20180057938A1 US 201715687839 A US201715687839 A US 201715687839A US 2018057938 A1 US2018057938 A1 US 2018057938A1
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/452—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by activating reactive gas streams before their introduction into the reaction chamber, e.g. by ionisation or addition of reactive species
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/301—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C23C16/303—Nitrides
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45502—Flow conditions in reaction chamber
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45512—Premixing before introduction in the reaction chamber
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/458—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber
- C23C16/4582—Rigid and flat substrates, e.g. plates or discs
- C23C16/4583—Rigid and flat substrates, e.g. plates or discs the substrate being supported substantially horizontally
- C23C16/4584—Rigid and flat substrates, e.g. plates or discs the substrate being supported substantially horizontally the substrate being rotated
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02538—Group 13/15 materials
- H01L21/0254—Nitrides
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
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- H—ELECTRICITY
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
Definitions
- the embodiments of the present invention relate to a vapor-phase growth method.
- GaN HEMT High Electron Mobility Transistor
- MOCVD Metal Organic Chemical Vapor Deposition
- trimethylaluminum (TMA) gas, trimethylgallium (TMG) gas, and a gas including ammonium are supplied as source gases into a chamber in which a wafer of Si or the like is placed.
- TMA trimethylaluminum
- TMG trimethylgallium
- a gas including ammonium are supplied as source gases into a chamber in which a wafer of Si or the like is placed.
- the supplied source gases are caused to react with one another on the heated wafer to cause the AlGaN layer to grow on the wafer.
- a substrate is placed on a support part provided in a reaction chamber and a source gas including an organic metal is supplied onto the substrate from a portion above the reaction chamber, while the substrate is rotated together with the support part around a rotation axis passing through a center of the substrate at a rotating speed of 1300 rpm or more and 2000 rpm or less, to cause a III-V semiconductor layer to grow on the substrate.
- FIG. 1 is a plan view illustrating an example of a vapor-phase growth device that can be applied to a vapor-phase growth method according to the present embodiment
- FIG. 2 is a cross-sectional view of the vapor-phase growth device of FIG. 1 ;
- FIG. 3 is a graph illustrating a first experimental example of the vapor-phase growth method
- FIG. 4 is a graph illustrating a second experimental example of the vapor-phase growth method.
- FIG. 5 is a graph illustrating a third experimental example of the vapor-phase growth method.
- FIG. 1 is a plan view illustrating an example of a vapor-phase growth device 1 that can be applied to a vapor-phase growth method according to the present embodiment.
- the vapor-phase growth device 1 of FIG. 1 is a single-wafer type epitaxial growth device that uses a MOCVD method. As illustrated in FIG. 1 , the vapor-phase growth device 1 includes four chambers 2 A to 2 D that are an example of a reaction chamber, a cassette chamber 3 , and a transfer chamber 4 .
- Each of the chambers 2 A to 2 D processes a wafer W that is an example of a substrate under a pressure less than atmospheric pressure.
- the chambers 2 A to 2 D are arranged straight along a transfer direction d in the transfer chamber 4 .
- the vapor-phase growth device 1 can efficiently process a plurality of wafers W because it includes the plural chambers 2 A to 2 D.
- the cassette chamber 3 includes a placing table 32 that allows a cassette 31 holding the plural wafers W to be placed thereon.
- the cassette 31 is made of a resin or aluminum, for example.
- the cassette chamber 3 is provided with a gate valve 33 .
- the cassette 31 can be transferred into the cassette chamber 3 from outside through the gate valve 33 .
- a pressure in the cassette chamber 3 can be reduced to a pressure less than atmospheric pressure by a vacuum pump (not illustrated), while the gate valve 33 is closed.
- the transfer chamber 4 is provided between the cassette chamber 3 and the chambers 2 A to 2 D.
- the wafer W is transferred in the transfer direction d between the cassette chamber 3 and the chambers 2 A to 2 D under a pressure less than atmospheric pressure. More specifically, the wafer W before epitaxial growth is transferred from the cassette chamber 3 to the chambers 2 A to 2 D, and the wafer W after epitaxial growth is transferred from the chambers 2 A to 2 D to the cassette chamber 3 .
- a robot arm 41 and a placing table 42 are provided in the transfer chamber 4 . The robot arm 41 can deliver and receive the wafer W to/from the cassette chamber 3 or the chambers 2 A to 2 D.
- the placing table 42 can move in the transfer direction d with the wafer W and the robot arm 41 placed thereon. Therefore, it is possible to move the robot arm 41 that has received the wafer W before epitaxial growth from the cassette chamber 3 to each of the chambers 2 A to 2 D by the placing table 42 , and to transfer the wafer W held by the robot arm 41 into the chambers 2 A to 2 D. Further, it is possible to move the robot arm 41 that has received the wafer W after epitaxial growth from each of the chambers 2 A to 2 D to the cassette chamber 3 by the placing table 42 , to collect the wafer W held by the robot arm 41 into the cassette chamber 3 .
- Gate valves 43 A to 43 E that can be opened and closed are provided between the cassette chamber 3 and the transfer chamber 4 and between the transfer chamber 4 and the chambers 2 A to 2 D.
- the gate valve 43 A By opening the gate valve 43 A, the wafer W can be moved between the cassette chamber 3 and the transfer chamber 4 .
- the gate valves 43 B to 43 E By opening each of the gate valves 43 B to 43 E, the wafer W can be moved between the transfer chamber 4 and a corresponding one of the chambers 2 A to 2 D.
- FIG. 2 is a cross-sectional view of the vapor-phase growth device 1 of FIG. 1 .
- FIG. 2 illustrates an internal configuration of each of the chambers 2 A to 2 D of the vapor-phase growth device 1 of FIG. 1 , together with an upstream gas channel and a downstream gas channel of the chambers 2 A to 2 D.
- the vapor-phase growth device 1 includes the above configuration and further includes a gas supply part 5 , a shower head 6 , a susceptor 7 that is an example of a support part, a rotary part 8 , a rotating mechanism 9 , a heater 10 , a gas discharger 11 , and an exhaust mechanism 12 .
- the gas supply part 5 is connected to the chambers 2 A to 2 D on a gas upstream side.
- the gas supply part 5 includes a plurality of reservoirs 5 a , a plurality of gas pipes 5 b , and a plurality of gas valves 5 c .
- Each of the reservoirs 5 a stores a gas or a gas liquid precursor therein.
- a source gas of the III-V semiconductor layer or its liquid precursor is stored in each reservoir 5 a .
- trimethylaluminum liquid, trimethylgallium liquid, and ammonium are stored in the respective reservoirs 5 a.
- Trimethylaluminum stored in the reservoir 5 a becomes a first source gas including trimethylaluminum (hereinafter, also “TMA gas”) as an example of a group III source gas by being subjected to bubbling, that is, being vaporized with a carrier gas, such as hydrogen gas.
- Trimethylgallium stored in the reservoir 5 a becomes a second source gas including trimethylgallium (hereinafter, also “TMG gas”) as an example of the group III source gas by being subjected to bubbling with a carrier gas, such as hydrogen gas.
- TMA gas trimethylaluminum
- TMG gas trimethylgallium
- the gas pipes 5 b connect each of the reservoirs 5 a and a gas introduction part 6 a to each other.
- the gas valves 5 c are provided in the gas pipes 5 b , respectively.
- Each gas valve 5 c can adjust the flow rate of a gas flowing in a corresponding gas pipe 5 b .
- a plurality of pipe configurations can be actually employed, for example, in which a plurality of gas pipes are joined, a single gas pipe branches to a plurality of gas pipes, and branching and joining of the gas pipes are combined.
- the gas introduction part 6 a is connected to the shower head 6 provided in an upper portion of the chambers 2 A to 2 D.
- the shower head 6 has a shower plate 61 on its bottom side.
- the shower plate 61 is provided with a plurality of gas outlets 62 .
- the shower plate 61 can be configured by using a metal source, for example, stainless steel or aluminum alloy.
- a plurality of gases respectively supplied from the gas pipes 5 b are introduced into the shower head 6 .
- the introduced gases are mixed in the shower head 6 , and are then supplied into the chambers 2 A to 2 D through the gas outlets 62 of the shower plate 61 .
- a plurality of gas channels extending laterally may be provided in the shower plate 61 , so that a plurality of types of gases are supplied to the wafer W in the chambers 2 A to 2 D while being separated from each other.
- the susceptor 7 supports the wafer W in the chambers 2 A to 2 D in such a manner that the wafer W is placed horizontally.
- the susceptor 7 is provided in an upper portion of the rotary part 8 , and supports the wafer W placed in a recess 7 a provided on an inner circumferential side of the susceptor 7 .
- the susceptor 7 has an annular shape having an opening at its center in the example of FIG. 2
- the susceptor 7 may be an approximately flat plate with no opening.
- the susceptor 7 supports a single wafer W in the example of FIG. 2
- the susceptor 7 may support a plurality of wafers W, for example, four wafers W.
- the rotary part 8 rotates in the chambers 2 A to 2 D around a rotation axis A that extends vertically, while holding the susceptor 7 .
- the rotation axis A passes through the center of the susceptor 7 and a center of the wafer W.
- the susceptor 7 held by the rotary part 8 rotates around the rotation axis A together with the wafer W supported by the susceptor 7 .
- the rotating mechanism 9 drives and rotates the rotary part 8 .
- the rotating mechanism 9 includes a driving source, such as a motor, a controller that controls the driving source, and a transmission member that transmits a driving force of the driving source to the rotary part 8 , such as a timing belt or a gear.
- the rotating mechanism 9 rotates the wafer W at a predetermined rotating speed.
- the rotating speed of the wafer W is controlled to be 1300 rpm or more and 2000 rpm or less in order to improve in-planar uniformity.
- the heater 10 heats the susceptor 7 and the wafer W from below.
- a specific heating method of the heater 10 is not particularly limited. For example, resistance heating, lamp heating, or induction heating may be employed.
- the gas discharger 11 discharges the source gases after reaction from the inside of the chambers 2 A to 2 D to outside.
- the exhaust mechanism 12 controls the inside of the chambers 2 A to 2 D to have a desired pressure by operations of an exhaust valve 12 a and a vacuum pump 12 b through the gas discharger 11 .
- a vapor-phase growth method that is, a deposition method that uses the single-wafer type vapor-phase growth device 1 configured in the above manner is described.
- an AlGaN layer is caused to grow as a III-V semiconductor layer by a MOCVD method.
- the description of a process of a semiconductor layer in a HEMT other than the AlGaN layer, such as an AlN layer, is omitted in the following description.
- the robot arm 41 and the placing table 42 in the transfer chamber 4 transfer the wafer W from the cassette chamber 3 to the chambers 2 A to 2 D through the gate valve 43 A and a corresponding one of the gate valves to 43 B to 43 E.
- the robot arm 41 then places the transferred wafer W on the susceptor 7 .
- An inert gas such as H 2 , N 2 , or Ar, is supplied into the chambers 2 A to 2 D at a predetermined flow rate from the gas introduction part 6 a through the shower head 6 and the gas outlets 62 .
- the gate valves 43 A to 43 E are closed.
- the exhaust mechanism 12 then exhausts air in the inside of the chambers 2 A to 2 D through the gas discharger 11 to adjust a pressure in the chambers 2 A to 2 D to a desired pressure.
- the wafer W is heated by the heater 10 to an epitaxial growth temperature, for example, 1000° C. or higher and 1100° C. or lower.
- the rotating mechanism 9 rotates the wafer W around the rotation axis A at a predetermined rotating speed via the rotary part 8 and the susceptor 7 .
- the gas supply part 5 supplies TMA gas and TMG gas into the chambers 2 A to 2 D, together with ammonium gas.
- TMA gas, TMG gas, and ammonium gas supplied from the gas supply part 5 are introduced into the shower head 6 provided in an upper portion of the chambers 2 A to 2 D, and are mixed in the shower head 6 .
- the mixture of TMA gas, TMG gas, and ammonium gas is discharged toward the wafer W from the gas outlets 62 of the shower plate 61 .
- the wafer W is heated to a predetermined temperature and is rotated at the predetermined rotating speed. With this operation, an AlGaN layer is formed on the wafer W.
- a region in a thickness direction on a surface of the wafer W, in which vapor phase reaction occurs is referred to as a boundary layer.
- a boundary layer When the rotating speed of the wafer W is low, it is considered that a thick, non-uniform boundary layer is formed on the wafer W.
- the boundary layer is thick, vapor phase reaction of the source gases in the boundary layer occurs before the source gases reach the wafer W. Therefore, a speed of growth is lowered.
- TMA gas for which vapor phase reaction can occur relatively easily and TMG gas for which vapor phase reaction hardly occurs are made to flow simultaneously to cause reaction with ammonium gas and deposition of the AlGaN layer.
- TMA and ammonium preferentially react with each other because of a behavior of gases in the boundary layer, so that TMA and ammonium form particles and are exhausted without contributing to growth of the AlGaN layer.
- a distribution is generated in vapor phase reaction, which causes not only the layer thickness but also an in-plane distribution of Al to be lowered.
- vapor phase reaction can proceed more easily in a case where the gases are mixed in the shower head 6 and are then supplied to the chambers 2 A to 2 D.
- the wafer W is rotated at a high rotating speed of 1300 rpm or more. Due to a combination of this high-speed rotation and a flow of the source gases falling down from the shower plate 61 toward the wafer W, it is possible to form a thin and uniform boundary layer on the wafer W.
- the rotating speed of the wafer W is preferably 1500 rpm or more, and is more preferably 1500 rpm or more and 1700 rpm or less.
- the thin and uniform boundary layer By forming the thin and uniform boundary layer, it is possible to suppress occurrence of vapor phase reaction of the source gases before the source gases reach the wafer W. Also, the thin boundary layer allows the source gases to be easily taken into the surface of the wafer W, so that the thin boundary layer can accelerate uniform vapor phase reaction on the surface of the wafer W. Further, the particles on the wafer W can be efficiently discharged from an area on the wafer W by a centrifugal force generated by high-speed rotation of the wafer W. That is, the source gases supplied onto the wafer W from a portion above the chambers 2 A to 2 D form the boundary layer on the wafer W, and are discharged from an outer periphery of the wafer W. With this operation, the AlGaN layer can be caused to grow with high in-plane uniformity on the surface of the wafer W.
- the single-wafer type vapor-phase growth device 1 is used in the vapor-phase growth method of the present embodiment, a more stable gas flow can be obtained as compared with a case of using a batch type vapor-phase growth device, and it is possible to cause the AlGaN layer to epitaxially grow stably.
- An underlying structure of the AlGaN layer is not particularly limited, as long as it allows the AlGaN layer to epitaxially grow.
- the underlying structure may be an AlN buffer layer formed on an AlN substrate that is an example of the wafer W.
- the vapor-phase growth method of the present embodiment can be also effectively applied to growth of a III-V semiconductor layer other than the AlGaN layer, for example, an AlN layer, a GaN layer, an InGaN layer, and a pGaN layer.
- FIG. 3 is a graph illustrating a first experimental example of the vapor-phase growth method.
- four rotating speeds of 800 rpm, 1000 rpm, 1200 rpm, and 1500 rpm were used as a rotating speed of the wafer W.
- an AlGaN layer was caused to epitaxially grow on the wafer W by a MOCVD method.
- the heating temperature of the wafer W by the heater 10 was set to 1060° C.
- the thickness of the AlGaN layer growing at each rotating speed was measured at each of a center of the wafer W, a position 20 mm away from the center, a position 40 mm away from the center, a position 60 mm away from the center, and a position 80 mm away from the center.
- An X-ray diffractometer was used in measurement of the thickness and a composition of the AlGaN layer.
- the measurement results of the thickness of the AlGaN layer are represented as a graph as illustrated in FIG. 3 .
- the horizontal axis represents a distance from the center of the wafer W
- the vertical axis represents the thickness of the AlGaN layer at each measurement position that is normalized by regarding the thickness of the AlGaN layer at the center of the wafer W as 1.
- a ratio of a maximum value max of the thickness of the AlGaN layer and a minimum value mix thereof was less than 0.96.
- min/max a ratio of a maximum value max of the thickness of the AlGaN layer and a minimum value mix thereof
- in-plane uniformity of the AlGaN layer was able to be improved to a satisfactory level by setting the rotating speed of the wafer W to 1300 rpm or more. Also, according to the first experimental example, it was confirmed that in-plane uniformity of the AlGaN layer was able to be improved more effectively by setting the rotating speed of the wafer W to 1500 rpm or more.
- FIG. 4 is a graph illustrating a second experimental example of the vapor-phase growth method.
- an AlGaN layer was caused to epitaxially grow on the wafer W by a MOCVD method in each of the four chambers 2 A to 2 D of the vapor-phase growth device 1 of FIG. 1 , while the wafer W was rotated at 1700 rpm.
- a heating temperature Tg of the wafer W by the heater 10 was set to 1030° C.
- the thickness of the AlGaN layer growing in each of the chambers 2 A to 2 D was measured at each of a center of the wafer W, a position 20 mm away from the center, a position 40 mm away from the center, a position 60 mm away from the center, a position 80 mm away from the center, and a position 90 mm away from the center.
- the measurement results of the thickness of the AlGaN layer are represented as a graph as illustrated in FIG. 4 .
- the horizontal axis represents a distance from the center of the wafer W
- the vertical axis represents the thickness of the AlGaN layer.
- FIG. 5 is a graph illustrating a third experimental example of the vapor-phase growth method. Growth conditions of an AlGaN layer in the third experimental example are the same as those in the second experimental example.
- an Al composition (%) in the AlGaN layer that epitaxially grew in each of the chambers 2 A to 2 D was measured at each of a center of the wafer W, a position 20 mm away from the center, a position 40 mm away from the center, a position 60 mm away from the center, a position 80 mm away from the center, and a position 90 mm away from the center.
- the measurement results of the Al composition in the AlGaN layer are represented as a graph as illustrated in FIG. 5 .
- the horizontal axis represents a distance from the center of the wafer W
- the vertical axis represents the Al composition in the AlGaN layer.
- the Al composition in the AlGaN layer was able to be uniformly controlled to be about 25% at each measurement position in all the four chambers 2 A to 2 D.
- the Al composition of about 25% indicates that favorable Al composition is obtained as a composition of the AlGaN layer.
- a rotating speed of the wafer W is set to 1300 rpm or more and 2000 rpm or less.
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Abstract
Description
- This application is based upon and claims the benefit of priority from Japanese Patent Application No. 2016-167132, filed on Aug. 29, 2016, the entire contents of which are incorporated herein by reference.
- The embodiments of the present invention relate to a vapor-phase growth method.
- In recent years, a GaN HEMT (High Electron Mobility Transistor) that is expected to have a high breakdown voltage and a very low ON resistance has been developed for use as a power semiconductor device, for example. In this GaN device, an AlGaN/GaN heterostructure is used, for example, and a MOCVD (Metal Organic Chemical Vapor Deposition) method is used for forming layers of the heterostructure.
- When an AlGaN layer is formed, trimethylaluminum (TMA) gas, trimethylgallium (TMG) gas, and a gas including ammonium are supplied as source gases into a chamber in which a wafer of Si or the like is placed. The supplied source gases are caused to react with one another on the heated wafer to cause the AlGaN layer to grow on the wafer.
- However, in a conventional MOCVD method, trimethylaluminum and ammonium react with each other in a vapor phase before reaching the wafer. Therefore, there has been a problem that it is difficult to ensure uniformity (hereinafter, also “in-plane uniformity”) of the thickness of the AlGaN layer and an Al concentration in the AlGaN layer in a wafer plane.
- It is an object of the present invention to provide a vapor-phase growth method that can improve in-plane uniformity of a III-V semiconductor layer.
- In a vapor-phase growth method according to an aspect of the present invention, a substrate is placed on a support part provided in a reaction chamber and a source gas including an organic metal is supplied onto the substrate from a portion above the reaction chamber, while the substrate is rotated together with the support part around a rotation axis passing through a center of the substrate at a rotating speed of 1300 rpm or more and 2000 rpm or less, to cause a III-V semiconductor layer to grow on the substrate.
-
FIG. 1 is a plan view illustrating an example of a vapor-phase growth device that can be applied to a vapor-phase growth method according to the present embodiment; -
FIG. 2 is a cross-sectional view of the vapor-phase growth device ofFIG. 1 ; -
FIG. 3 is a graph illustrating a first experimental example of the vapor-phase growth method; -
FIG. 4 is a graph illustrating a second experimental example of the vapor-phase growth method; and -
FIG. 5 is a graph illustrating a third experimental example of the vapor-phase growth method. - An embodiment of the present invention will now be explained below with reference to the accompanying drawings. The present invention is not limited to the embodiment.
-
FIG. 1 is a plan view illustrating an example of a vapor-phase growth device 1 that can be applied to a vapor-phase growth method according to the present embodiment. The vapor-phase growth device 1 ofFIG. 1 is a single-wafer type epitaxial growth device that uses a MOCVD method. As illustrated inFIG. 1 , the vapor-phase growth device 1 includes fourchambers 2A to 2D that are an example of a reaction chamber, acassette chamber 3, and atransfer chamber 4. - Each of the
chambers 2A to 2D processes a wafer W that is an example of a substrate under a pressure less than atmospheric pressure. Thechambers 2A to 2D are arranged straight along a transfer direction d in thetransfer chamber 4. The vapor-phase growth device 1 can efficiently process a plurality of wafers W because it includes theplural chambers 2A to 2D. - The
cassette chamber 3 includes a placing table 32 that allows acassette 31 holding the plural wafers W to be placed thereon. Thecassette 31 is made of a resin or aluminum, for example. Thecassette chamber 3 is provided with agate valve 33. Thecassette 31 can be transferred into thecassette chamber 3 from outside through thegate valve 33. A pressure in thecassette chamber 3 can be reduced to a pressure less than atmospheric pressure by a vacuum pump (not illustrated), while thegate valve 33 is closed. - The
transfer chamber 4 is provided between thecassette chamber 3 and thechambers 2A to 2D. In thetransfer chamber 4, the wafer W is transferred in the transfer direction d between thecassette chamber 3 and thechambers 2A to 2D under a pressure less than atmospheric pressure. More specifically, the wafer W before epitaxial growth is transferred from thecassette chamber 3 to thechambers 2A to 2D, and the wafer W after epitaxial growth is transferred from thechambers 2A to 2D to thecassette chamber 3. Arobot arm 41 and a placing table 42 are provided in thetransfer chamber 4. Therobot arm 41 can deliver and receive the wafer W to/from thecassette chamber 3 or thechambers 2A to 2D. The placing table 42 can move in the transfer direction d with the wafer W and therobot arm 41 placed thereon. Therefore, it is possible to move therobot arm 41 that has received the wafer W before epitaxial growth from thecassette chamber 3 to each of thechambers 2A to 2D by the placing table 42, and to transfer the wafer W held by therobot arm 41 into thechambers 2A to 2D. Further, it is possible to move therobot arm 41 that has received the wafer W after epitaxial growth from each of thechambers 2A to 2D to thecassette chamber 3 by the placing table 42, to collect the wafer W held by therobot arm 41 into thecassette chamber 3. -
Gate valves 43A to 43E that can be opened and closed are provided between thecassette chamber 3 and thetransfer chamber 4 and between thetransfer chamber 4 and thechambers 2A to 2D. By opening thegate valve 43A, the wafer W can be moved between thecassette chamber 3 and thetransfer chamber 4. Also, by opening each of thegate valves 43B to 43E, the wafer W can be moved between thetransfer chamber 4 and a corresponding one of thechambers 2A to 2D. -
FIG. 2 is a cross-sectional view of the vapor-phase growth device 1 ofFIG. 1 .FIG. 2 illustrates an internal configuration of each of thechambers 2A to 2D of the vapor-phase growth device 1 ofFIG. 1 , together with an upstream gas channel and a downstream gas channel of thechambers 2A to 2D. - As illustrated in
FIG. 2 , the vapor-phase growth device 1 includes the above configuration and further includes agas supply part 5, ashower head 6, asusceptor 7 that is an example of a support part, a rotary part 8, arotating mechanism 9, aheater 10, agas discharger 11, and anexhaust mechanism 12. - The
gas supply part 5 is connected to thechambers 2A to 2D on a gas upstream side. Thegas supply part 5 includes a plurality ofreservoirs 5 a, a plurality ofgas pipes 5 b, and a plurality ofgas valves 5 c. Each of thereservoirs 5 a stores a gas or a gas liquid precursor therein. When a III-V semiconductor layer is caused to grow on the wafer W, a source gas of the III-V semiconductor layer or its liquid precursor is stored in eachreservoir 5 a. For example, when an AlGaN layer is caused to grow as the III-V semiconductor layer, trimethylaluminum liquid, trimethylgallium liquid, and ammonium are stored in therespective reservoirs 5 a. - Trimethylaluminum stored in the
reservoir 5 a becomes a first source gas including trimethylaluminum (hereinafter, also “TMA gas”) as an example of a group III source gas by being subjected to bubbling, that is, being vaporized with a carrier gas, such as hydrogen gas. Trimethylgallium stored in thereservoir 5 a becomes a second source gas including trimethylgallium (hereinafter, also “TMG gas”) as an example of the group III source gas by being subjected to bubbling with a carrier gas, such as hydrogen gas. When an AlGaN layer is caused to grow, ammonium gas that is an example of a third source gas, that is, a group V source gas is supplied to thechambers 2A to 2D while TMA gas and TMG gas are supplied. - The
gas pipes 5 b connect each of thereservoirs 5 a and agas introduction part 6 a to each other. Thegas valves 5 c are provided in thegas pipes 5 b, respectively. Eachgas valve 5 c can adjust the flow rate of a gas flowing in acorresponding gas pipe 5 b. A plurality of pipe configurations can be actually employed, for example, in which a plurality of gas pipes are joined, a single gas pipe branches to a plurality of gas pipes, and branching and joining of the gas pipes are combined. - The
gas introduction part 6 a is connected to theshower head 6 provided in an upper portion of thechambers 2A to 2D. Theshower head 6 has ashower plate 61 on its bottom side. Theshower plate 61 is provided with a plurality ofgas outlets 62. Theshower plate 61 can be configured by using a metal source, for example, stainless steel or aluminum alloy. A plurality of gases respectively supplied from thegas pipes 5 b are introduced into theshower head 6. The introduced gases are mixed in theshower head 6, and are then supplied into thechambers 2A to 2D through thegas outlets 62 of theshower plate 61. A plurality of gas channels extending laterally may be provided in theshower plate 61, so that a plurality of types of gases are supplied to the wafer W in thechambers 2A to 2D while being separated from each other. - The
susceptor 7 supports the wafer W in thechambers 2A to 2D in such a manner that the wafer W is placed horizontally. Thesusceptor 7 is provided in an upper portion of the rotary part 8, and supports the wafer W placed in arecess 7 a provided on an inner circumferential side of thesusceptor 7. Although thesusceptor 7 has an annular shape having an opening at its center in the example ofFIG. 2 , thesusceptor 7 may be an approximately flat plate with no opening. Further, although thesusceptor 7 supports a single wafer W in the example ofFIG. 2 , thesusceptor 7 may support a plurality of wafers W, for example, four wafers W. - The rotary part 8 rotates in the
chambers 2A to 2D around a rotation axis A that extends vertically, while holding thesusceptor 7. The rotation axis A passes through the center of thesusceptor 7 and a center of the wafer W. By rotation of the rotary part 8, thesusceptor 7 held by the rotary part 8 rotates around the rotation axis A together with the wafer W supported by thesusceptor 7. - The
rotating mechanism 9 drives and rotates the rotary part 8. For example, therotating mechanism 9 includes a driving source, such as a motor, a controller that controls the driving source, and a transmission member that transmits a driving force of the driving source to the rotary part 8, such as a timing belt or a gear. Therotating mechanism 9 rotates the wafer W at a predetermined rotating speed. - During formation of a III-V semiconductor layer described later, the rotating speed of the wafer W is controlled to be 1300 rpm or more and 2000 rpm or less in order to improve in-planar uniformity.
- The
heater 10 heats thesusceptor 7 and the wafer W from below. A specific heating method of theheater 10 is not particularly limited. For example, resistance heating, lamp heating, or induction heating may be employed. - The
gas discharger 11 discharges the source gases after reaction from the inside of thechambers 2A to 2D to outside. - The
exhaust mechanism 12 controls the inside of thechambers 2A to 2D to have a desired pressure by operations of anexhaust valve 12 a and avacuum pump 12 b through thegas discharger 11. - A vapor-phase growth method, that is, a deposition method that uses the single-wafer type vapor-
phase growth device 1 configured in the above manner is described. In the vapor-phase growth method described below, an AlGaN layer is caused to grow as a III-V semiconductor layer by a MOCVD method. Further, the description of a process of a semiconductor layer in a HEMT other than the AlGaN layer, such as an AlN layer, is omitted in the following description. - The
robot arm 41 and the placing table 42 in thetransfer chamber 4 transfer the wafer W from thecassette chamber 3 to thechambers 2A to 2D through thegate valve 43A and a corresponding one of the gate valves to 43B to 43E. Therobot arm 41 then places the transferred wafer W on thesusceptor 7. - An inert gas, such as H2, N2, or Ar, is supplied into the
chambers 2A to 2D at a predetermined flow rate from thegas introduction part 6 a through theshower head 6 and thegas outlets 62. After the wafer W is placed on thesusceptor 7, thegate valves 43A to 43E are closed. Theexhaust mechanism 12 then exhausts air in the inside of thechambers 2A to 2D through thegas discharger 11 to adjust a pressure in thechambers 2A to 2D to a desired pressure. - The wafer W is heated by the
heater 10 to an epitaxial growth temperature, for example, 1000° C. or higher and 1100° C. or lower. - The
rotating mechanism 9 rotates the wafer W around the rotation axis A at a predetermined rotating speed via the rotary part 8 and thesusceptor 7. - While the wafer W is rotated, the
gas supply part 5 supplies TMA gas and TMG gas into thechambers 2A to 2D, together with ammonium gas. - TMA gas, TMG gas, and ammonium gas supplied from the
gas supply part 5 are introduced into theshower head 6 provided in an upper portion of thechambers 2A to 2D, and are mixed in theshower head 6. The mixture of TMA gas, TMG gas, and ammonium gas is discharged toward the wafer W from thegas outlets 62 of theshower plate 61. - In this manner, while source gases are supplied onto the wafer W at a predetermined flow rate, the wafer W is heated to a predetermined temperature and is rotated at the predetermined rotating speed. With this operation, an AlGaN layer is formed on the wafer W.
- Here, a region in a thickness direction on a surface of the wafer W, in which vapor phase reaction occurs, is referred to as a boundary layer. When the rotating speed of the wafer W is low, it is considered that a thick, non-uniform boundary layer is formed on the wafer W. When the boundary layer is thick, vapor phase reaction of the source gases in the boundary layer occurs before the source gases reach the wafer W. Therefore, a speed of growth is lowered. Further, in order to form an AlGaN layer, TMA gas for which vapor phase reaction can occur relatively easily and TMG gas for which vapor phase reaction hardly occurs are made to flow simultaneously to cause reaction with ammonium gas and deposition of the AlGaN layer. Therefore, TMA and ammonium preferentially react with each other because of a behavior of gases in the boundary layer, so that TMA and ammonium form particles and are exhausted without contributing to growth of the AlGaN layer. In this manner, a distribution is generated in vapor phase reaction, which causes not only the layer thickness but also an in-plane distribution of Al to be lowered. Particularly, vapor phase reaction can proceed more easily in a case where the gases are mixed in the
shower head 6 and are then supplied to thechambers 2A to 2D. - On the other hand, in the present embodiment, the wafer W is rotated at a high rotating speed of 1300 rpm or more. Due to a combination of this high-speed rotation and a flow of the source gases falling down from the
shower plate 61 toward the wafer W, it is possible to form a thin and uniform boundary layer on the wafer W. - When the rotating speed of the wafer W is lower than 1300 rpm, it is difficult to ensure in-plane uniformity of the AlGaN layer. Meanwhile, when the rotating speed is higher than 2000 rpm, vibration, slippage, jump, or the like caused by small misalignment of the wafer W or the
rotating mechanism 9, or the like occurs, and makes stable deposition difficult. - Therefore, by setting the rotating speed of the wafer W to 1300 rpm or more and 2000 rpm or less, it is possible to improve the in-plane uniformity of the AlGaN layer stably. Further, by setting the rotating speed to 1300 rpm or more and 2000 rpm or less, uniformity of an Al composition in a wafer plane can be also improved, in addition to the in-plane uniformity of the thickness of the AlGaN layer, as described later. The rotating speed of the wafer W is preferably 1500 rpm or more, and is more preferably 1500 rpm or more and 1700 rpm or less.
- By forming the thin and uniform boundary layer, it is possible to suppress occurrence of vapor phase reaction of the source gases before the source gases reach the wafer W. Also, the thin boundary layer allows the source gases to be easily taken into the surface of the wafer W, so that the thin boundary layer can accelerate uniform vapor phase reaction on the surface of the wafer W. Further, the particles on the wafer W can be efficiently discharged from an area on the wafer W by a centrifugal force generated by high-speed rotation of the wafer W. That is, the source gases supplied onto the wafer W from a portion above the
chambers 2A to 2D form the boundary layer on the wafer W, and are discharged from an outer periphery of the wafer W. With this operation, the AlGaN layer can be caused to grow with high in-plane uniformity on the surface of the wafer W. - Further, because the single-wafer type vapor-
phase growth device 1 is used in the vapor-phase growth method of the present embodiment, a more stable gas flow can be obtained as compared with a case of using a batch type vapor-phase growth device, and it is possible to cause the AlGaN layer to epitaxially grow stably. - An underlying structure of the AlGaN layer is not particularly limited, as long as it allows the AlGaN layer to epitaxially grow. For example, the underlying structure may be an AlN buffer layer formed on an AlN substrate that is an example of the wafer W.
- The vapor-phase growth method of the present embodiment can be also effectively applied to growth of a III-V semiconductor layer other than the AlGaN layer, for example, an AlN layer, a GaN layer, an InGaN layer, and a pGaN layer.
- Experimental examples of a vapor-phase growth method are described.
-
FIG. 3 is a graph illustrating a first experimental example of the vapor-phase growth method. In the first experimental example, four rotating speeds of 800 rpm, 1000 rpm, 1200 rpm, and 1500 rpm were used as a rotating speed of the wafer W. At each rotating speed, an AlGaN layer was caused to epitaxially grow on the wafer W by a MOCVD method. The heating temperature of the wafer W by theheater 10 was set to 1060° C. The thickness of the AlGaN layer growing at each rotating speed was measured at each of a center of the wafer W, aposition 20 mm away from the center, aposition 40 mm away from the center, aposition 60 mm away from the center, and aposition 80 mm away from the center. An X-ray diffractometer was used in measurement of the thickness and a composition of the AlGaN layer. The measurement results of the thickness of the AlGaN layer are represented as a graph as illustrated inFIG. 3 . InFIG. 3 , the horizontal axis represents a distance from the center of the wafer W, and the vertical axis represents the thickness of the AlGaN layer at each measurement position that is normalized by regarding the thickness of the AlGaN layer at the center of the wafer W as 1. - As illustrated in
FIG. 3 , when the rotating speed of the wafer W was 800 rpm, 1000 rpm, and 1200 rpm, a ratio of a maximum value max of the thickness of the AlGaN layer and a minimum value mix thereof (hereinafter, also “min/max”) was less than 0.96. For example, in order to obtain favorable HEMT characteristics, it is preferable that in-plane uniformity of the AlGaN layer, that is, min/max is 0.96 or more. However, when the rotating speed was 800 rpm, 1000 rpm, and 1200 rpm, this condition was not satisfied. On the other hand, when the rotating speed of the wafer W was 1500 rpm, it was possible to obtain min/max larger than 0.96. It can be estimated that the above condition can be satisfied when the rotating speed is about 1300 rpm. - Therefore, according to the first experimental example, it was confirmed that in-plane uniformity of the AlGaN layer was able to be improved to a satisfactory level by setting the rotating speed of the wafer W to 1300 rpm or more. Also, according to the first experimental example, it was confirmed that in-plane uniformity of the AlGaN layer was able to be improved more effectively by setting the rotating speed of the wafer W to 1500 rpm or more.
-
FIG. 4 is a graph illustrating a second experimental example of the vapor-phase growth method. In the second experimental example, an AlGaN layer was caused to epitaxially grow on the wafer W by a MOCVD method in each of the fourchambers 2A to 2D of the vapor-phase growth device 1 ofFIG. 1 , while the wafer W was rotated at 1700 rpm. A heating temperature Tg of the wafer W by theheater 10 was set to 1030° C. The thickness of the AlGaN layer growing in each of thechambers 2A to 2D was measured at each of a center of the wafer W, aposition 20 mm away from the center, aposition 40 mm away from the center, aposition 60 mm away from the center, aposition 80 mm away from the center, and aposition 90 mm away from the center. The measurement results of the thickness of the AlGaN layer are represented as a graph as illustrated inFIG. 4 . InFIG. 4 , the horizontal axis represents a distance from the center of the wafer W, and the vertical axis represents the thickness of the AlGaN layer. - As illustrated in
FIG. 4 , it was found that in all the fourchambers 2A to 2D, the difference between the maximum thickness and the minimum thickness of the AlGaN layer was able to be suppressed within 1 nm. This is sufficiently favorable as in-plane uniformity. Further, the results inFIG. 4 show that in-plane uniformity in each of thechambers 2A to 2D is favorable, and also show that interplanar uniformity that is uniformity of the thickness of the AlGaN layer among thechambers 2A to 2D is also favorable. -
FIG. 5 is a graph illustrating a third experimental example of the vapor-phase growth method. Growth conditions of an AlGaN layer in the third experimental example are the same as those in the second experimental example. In the third experimental example, an Al composition (%) in the AlGaN layer that epitaxially grew in each of thechambers 2A to 2D was measured at each of a center of the wafer W, aposition 20 mm away from the center, aposition 40 mm away from the center, aposition 60 mm away from the center, aposition 80 mm away from the center, and aposition 90 mm away from the center. - The measurement results of the Al composition in the AlGaN layer are represented as a graph as illustrated in
FIG. 5 . InFIG. 5 , the horizontal axis represents a distance from the center of the wafer W, and the vertical axis represents the Al composition in the AlGaN layer. - As illustrated in
FIG. 5 , it was found that the Al composition in the AlGaN layer was able to be uniformly controlled to be about 25% at each measurement position in all the fourchambers 2A to 2D. The Al composition of about 25% indicates that favorable Al composition is obtained as a composition of the AlGaN layer. - As described above, according to the present embodiment, it is possible to improve in-plane uniformity of a III-V semiconductor layer by using a MOCVD method in which a rotating speed of the wafer W is set to 1300 rpm or more and 2000 rpm or less.
- The embodiment described above has been presented by way of example only and is not intended to limit the scope of the invention. The embodiment can be implemented in a variety of other forms, and various omissions, substitutions and changes can be made without departing from the spirit of the invention. The embodiment and modifications thereof are included in the scope of invention described in the claims and their equivalents as well as the scope and the spirit of the invention.
Claims (10)
Applications Claiming Priority (2)
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|---|---|---|---|
| JP2016-167132 | 2016-08-29 | ||
| JP2016167132A JP6786307B2 (en) | 2016-08-29 | 2016-08-29 | Vapor deposition method |
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| US20180057938A1 true US20180057938A1 (en) | 2018-03-01 |
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| US10351949B2 (en) | 2016-12-21 | 2019-07-16 | Nuflare Technology, Inc. | Vapor phase growth method |
| US11072856B2 (en) | 2018-03-01 | 2021-07-27 | Nuflare Technology, Inc. | Vapor phase growth method |
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| US10351949B2 (en) | 2016-12-21 | 2019-07-16 | Nuflare Technology, Inc. | Vapor phase growth method |
| US11072856B2 (en) | 2018-03-01 | 2021-07-27 | Nuflare Technology, Inc. | Vapor phase growth method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2018037456A (en) | 2018-03-08 |
| KR102072704B1 (en) | 2020-02-03 |
| TWI685883B (en) | 2020-02-21 |
| TW201820417A (en) | 2018-06-01 |
| TW201946115A (en) | 2019-12-01 |
| JP6786307B2 (en) | 2020-11-18 |
| KR20180025194A (en) | 2018-03-08 |
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